EP3026175B1 - Papier à haut pouvoir couvrant - Google Patents

Papier à haut pouvoir couvrant Download PDF

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Publication number
EP3026175B1
EP3026175B1 EP14195070.9A EP14195070A EP3026175B1 EP 3026175 B1 EP3026175 B1 EP 3026175B1 EP 14195070 A EP14195070 A EP 14195070A EP 3026175 B1 EP3026175 B1 EP 3026175B1
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EP
European Patent Office
Prior art keywords
resin
pigment
paper
decorative
particles
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EP14195070.9A
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German (de)
English (en)
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EP3026175A1 (fr
Inventor
Marina Skotkin
Andreas Dr. Overberg
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Schoeller Technocell GmbH and Co KG
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Schoeller Technocell GmbH and Co KG
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Application filed by Schoeller Technocell GmbH and Co KG filed Critical Schoeller Technocell GmbH and Co KG
Priority to EP14195070.9A priority Critical patent/EP3026175B1/fr
Priority to US14/941,977 priority patent/US9976257B2/en
Priority to JP2015231348A priority patent/JP2016102288A/ja
Priority to CN201510849841.4A priority patent/CN105648838A/zh
Publication of EP3026175A1 publication Critical patent/EP3026175A1/fr
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Publication of EP3026175B1 publication Critical patent/EP3026175B1/fr
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/51—Triazines, e.g. melamine
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57—Polyureas; Polyurethanes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/26—Agents rendering paper transparent or translucent
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/28—Colorants ; Pigments or opacifying agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/006—Substrates for image-receiving members; Image-receiving members comprising only one layer
    • G03G7/0066—Inorganic components thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/006—Substrates for image-receiving members; Image-receiving members comprising only one layer
    • G03G7/0073—Organic components thereof

Definitions

  • the invention relates to a paper, in particular a decorative base paper, for applications in which a high opacity of the paper is required, and decorative coating materials produced using the decorative base paper.
  • Decorative coating materials are preferably used for surface coating in the production of furniture and in interior fittings, in particular laminate floors.
  • Decorative paper / decorative film is understood as meaning resin-impregnated or resin-impregnated and surface-treated, printed or unprinted papers.
  • Decorative papers / decorative foils are glued or glued with a carrier plate.
  • urea glues or polyvinyl acetate (PVAC) glues are used for gluing the decorative films on wood materials such as chipboard or MDF board.
  • High pressure laminates are laminates produced by pressing several impregnated, laminated papers together.
  • the structure of these laminates generally consists of a highest surface resistance generating transparent overlay sheet (overlay), a resin-impregnated decorative paper and one or more phenolbehechen kraft papers.
  • overlay transparent overlay sheet
  • resin-impregnated decorative paper resin-impregnated decorative paper
  • phenolbehechen kraft papers resin-impregnated decorative paper
  • hardboard and chipboard and plywood are used.
  • the decorative paper impregnated with synthetic resin is pressed directly with a base, for example a chipboard, using a low pressure.
  • the decorative paper used in the above-mentioned coating materials is used white or colored with or without additional imprint.
  • the so-called decorative base papers serving as starting materials must fulfill certain requirements. These include high opacity for better coverage of the pad, uniform formation and grammage of the sheet for uniform resin pickup, high lightfastness, high purity and uniformity of color for good reproducibility of the pattern to be printed, high wet strength for smooth impregnation (impregnation), respectively Absorbency to obtain the required resin saturation level, dry strength, which in Umrollvor réellen in the Paper machine and when printing in the printing press is important. Furthermore, the gap strength (strength in the z direction) is of particular importance, since it is a measure of how well the decorative base paper can be processed. For example, the glued decorative paper / decorative foil must not fray during processing steps such as sawing or drilling.
  • Decorative base papers generally consist of bright white sulphate pulps, predominantly of hardwood pulp, with a high proportion of pigments and fillers, as well as wet strength agents, retention aids and fixatives.
  • Decorative base papers differ from conventional papers due to the much higher filler content and the lack of paper sizing or surface sizing with known sizing agents such as alkylketene dimers.
  • the opacity is one of the most important properties of decorative raw paper. This characterizes the covering capacity with respect to the base.
  • the opacity is caused by light scattering on the pigment particles.
  • pigment particles having a specific size and a narrow size distribution.
  • the light-scattering pigment particles are distributed as uniformly as possible in the medium to be rendered opaque. Clusters of pigment particles reduce light scattering.
  • the US 4,608,401 describes a method for encapsulating titanium dioxide particles with a water-insoluble polymer in an aqueous suspension and the use of the resulting particles in paints.
  • DE 199 61 964 A1 describes a process for preparing an aqueous dispersion of composite particles consisting of a finely divided inorganic solid and a polymer.
  • the described teachings for use in Dekorrohpapieren not be used advantageously because on the one hand the achievable distances between the pigment particles are too low and on the other hand, the pore volume of Dekorrohpapiers is reduced by the soft polymer latex components of these pigment preparations, which adversely affects the impregnation of the base paper.
  • the DE 10 2013 100353 A1 describes a reactive composite of titanium dioxide, a binder and at least one carrier.
  • the support is preferably an inorganic material to which the titania particles are coated with a reactive binder to form the so-called reactive composite.
  • At least 80% by weight of the titanium dioxide particles preferably have a particle size of less than 5 ⁇ m and at least 80% by mass of the carrier particles preferably have a particle size of less than 50 ⁇ m.
  • the entire composite has a particle size of greater than 63 microns.
  • the DE 697 12 421 T2 describes a matte-coated paper having a surface coating containing both organic pigment particles and calcium carbonate particles.
  • the DE 10 2010 051 382 A1 describes the impregnation of a paper with a mixture of thermosetting curing impregnating resin and pigment.
  • the JP 2007 270 388 A describes a matte coated white paper with low gloss that does not cause stains when rubbed with ink, such as another sheet.
  • the surface coating comprises a pigment and an adhesive, for example a urethane resin or (meth) acrylate resin particle.
  • the EP 1 207 233 A2 describes a decorative paper with high opacity with a mixture of two pigments, namely titanium dioxide and talc a certain particle size distribution. The addition of talc is intended to reduce the use of titanium dioxide while maintaining the same opacity of the sheet.
  • the invention is therefore based on the object of producing a decorative base paper with a high opacity and at the same time reduced whiteness and / or color pigment content.
  • a paper in particular a decorative base paper for decorative coating materials, comprising Cellulose fibers and pigment resin particles, wherein the pigment resin particles contain a pigment and a hardening resin and the average particle size of the pigment resin particles is 1 to 30 ⁇ m, wherein the mass ratio of pigment to resin in the pigment resin particles is 1: 1 to 1:10 is.
  • the opacity of the decorative base paper according to the invention is significantly increased compared to a conventional decorative base paper with the same amount of pigment particles in conventional preparation.
  • the invention furthermore relates to a decor paper or decorative film containing such a decorative base paper.
  • the proportion of titanium dioxide in the paper can be significantly reduced while maintaining a uniformly high opacity. It is furthermore surprising that with up to 60% pigment resin parts a high material input can be introduced into the leaf structure, without significantly affecting the desired strength. It appears that the increase in opacity depends on the particle size of the pigment-resin particles.
  • a further advantage of the paper according to the invention is that in the further processing up to 40% impregnation resin can be saved.
  • the decorative base paper according to the invention is neither sized in the mass nor provided with a surface sizing. It contains essentially pulp, pigment and optionally a filler and conventional additives. Common additives may be wet strength agents, retention aids and fixatives.
  • Decorative base papers differ from common papers due to the much higher filler content or pigment content in the paper and the lack of standard paper sizing or surface sizing on paper. A decorative base paper therefore has absorption capacity for an impregnating resin.
  • Softwood pulps long fiber pulps
  • / or hardwood pulps short fiber pulps
  • the use of cotton fibers and mixtures thereof with the aforementioned types of pulp can also be used.
  • 100% by weight hardwood pulp has proven to be advantageous.
  • the quantities are based on the mass of the pulps (atro).
  • the pulp mixture may contain a proportion of cationically modified pulp fibers of at least 5% by weight, based on the weight of the pulp mixture.
  • a proportion of 10 to 50% by weight, in particular 10 to 20% by weight, of the cationically modified pulp in the pulp mixture has proved to be particularly advantageous.
  • the cationic modification of the pulp fibers can be accomplished by reaction of the fibers with an epichlorohydrin resin and a tertiary amine or by reaction with quaternary ammonium chlorides such as chlorohydroxypropyltrimethylammonium chloride or glycidyltrimethylammonium chloride. Cationically modified pulps and their preparation are for example made THE PAPER, Issue 12 (1980) p.575-579 known.
  • the pigment resin particles contained in the paper of the present invention contain a pigment and a resin.
  • the pigment resin particles have an average particle size of from 1 to 30 .mu.m, preferably from 2 to 10 .mu.m and more preferably from 2 to 5 .mu.m, for example about 3 .mu.m
  • the mass ratio of pigment to resin in the pigment resin particles is 1:10 to 1: 1, preferably 1: 7 to 1: 3.
  • the mass ratio of pigment to resin in the pigment resin particles in the case of using titanium dioxide as a pigment is 1: 1 to 1: 4, preferably about 1: 2.5.
  • any other pigment to resin ratios are also conceivable, as long as the desired high opacity of the decorative base paper is achieved.
  • pigments refers to finely divided inorganic or organic substances which are obtained naturally or synthetically and which are useful for achieving opacity, for coloring purposes or as a filler in paper.
  • Suitable color pigments for the preparation of the pigment resin particles present in the decorative base paper according to the invention are preferably mineral pigments which are used to increase the opacity in paints and coatings, in sheet-like materials such as paper or plastic films.
  • Such pigments may be, for example, kaolins, precipitated calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, silica, alumina, iron oxide, calcium carbonate in its natural form, such as limestone, marble or dolomite, and mixtures thereof.
  • titanium dioxide is preferred as a white pigment for many applications. This applies in particular to use in decorative base papers.
  • titania used in decorative papers can be usually used.
  • Such titanium dioxides are commercially available and can be used as a rutile or anatase type. Rutile-type titanium dioxides are preferred.
  • Exemplary commercially available titanium dioxides are Ti-Pure® R-796 +, Ti-Pure® R 902 from DuPont, KRONOS 2800 and KRONOS 2305.
  • the particle size of the pigments in the pigment resin particles used according to the invention is in the range from 100 nm to 3 .mu.m, preferably in the range from 200 nm to 1 .mu.m.
  • particle size is understood to mean the diameter of a sphere which is the same volume as the particle.
  • the pigment resin particles contain a substantially cured resin in addition to the pigment.
  • This resin is preferably a thermosetting resin.
  • Substantially cured means that the resin is present in more than 80%, preferably more than 90%, preferably 95%, more preferably more than 99%, in particular 100% cured. Substantially cured also means that the resin does not chemically bond with the cellulosic fibers.
  • suitable thermosetting resins for example, melamine-formaldehyde resins, melamine-urea-formaldehyde resins, phenol-formaldehyde resins, urea resins, polyurethanes and mixtures thereof can be used. But it is also the use of other thermosetting resins conceivable.
  • Urea-formaldehyde resins are particularly preferably used as thermosetting resins, with curing in the preparation of the pigment resin particles being carried out at a pH of from 3 to 6.
  • Commercially available crosslinking agents can also be used to cure the resin.
  • Other suitable polymers as the resin component of the pigment resin particles are those based on polyacrylic or polyacrylomethyl esters, polyvinyl acetate, polyvinyl chloride and mixtures thereof.
  • the preparation of the pigment-resin particles is preferably carried out in such a way that a stable aqueous dispersion of the pigment particles is introduced and this is subsequently mixed with an aqueous preparation of the monomers or oligomers of the resin.
  • concentration of the pigment particles in the dispersion may be 5 to 50% by mass based on the weight of the dispersion.
  • a dispersing aid stabilizer
  • Suitable examples are steric, electrostatic and electrosteric stabilizers.
  • the stabilizer types Byk 154 and Calgon neu are cited here.
  • the dispersion of the pigment particles may contain other additives, such as rheology aids, UV stabilizers, biocides and other additives.
  • the curing of the resin in the aqueous medium is carried out by lowering the pH in the acidic range and possibly an increase in the temperature of the mixture.
  • the thus obtained slurry (dispersion) of pigment resin particles is dried.
  • the drying can be done in a convection oven.
  • the drying temperature may preferably be 95 ° C to 130 ° C.
  • lower and higher temperatures can also be set for drying, as long as the properties of the dispersion are not impaired, in particular as long as there is no change in the color of the dispersion.
  • An essential step in the provision of the pigment resin particles is the adjustment of particle size.
  • the pigment resin particles present after drying in the form of chips are mechanically comminuted for this purpose.
  • the average particle size of the pigment resin particles is less than 5 microns or less than 4 microns, more preferably less than 3 microns.
  • the particle size was measured by laser scattering.
  • the comminution may preferably be carried out in two stages, first a coarse comminution and then grinding to the desired particle size.
  • the mechanical comminution can be carried out by all known comminution methods. Dry or wet grinding with known milling units or a spray drying or fluidized bed drying is preferred. The comminution methods can also be combined or applied one after the other. For example, a fine powder having an average particle size smaller than 50 ⁇ m can be obtained by dry milling. The desired average particle sizes of the pigment resin particles of up to about 3 microns can be adjusted for example by subsequent wet grinding with a drum mill or stirred ball mill.
  • the paper or decorative base paper according to the invention may, in addition to the pigment resin particles, further contain other mineral and non-mineral fillers.
  • Decorative base papers can be produced on a Fourdrinier paper machine or a Yankee paper machine.
  • the pulp mixture can be ground at a consistency of 2 to 5 wt .-% to a freeness of 10 to 45 ° SR.
  • fillers such as titanium dioxide and talc, and wet strength agents can be added and mixed well with the pulp mixture.
  • the resulting thick stock can be diluted to a stock consistency of about 1% and, if necessary, further auxiliaries such as retention aids, defoamers, aluminum sulfate and other auxiliaries mentioned above are mixed. This thin material is fed to the wire section via the headbox of the paper machine.
  • a non-woven fabric is formed and, after dewatering, the base paper is obtained, which is subsequently dried.
  • the basis weights of the papers produced can be 15 to 300 g / m 2 .
  • particularly suitable are base papers having a basis weight of 40 to 100 g / m 2 .
  • the decorative base papers are impregnated or impregnated with synthetic resin dispersions customary for this purpose.
  • synthetic resin dispersions customary for this purpose.
  • synthetic resin dispersions include, for example, melamine-formaldehyde resins, melamine-urea-formaldehyde resins, phenol-formaldehyde resins, urea resins, polyurethanes and mixtures thereof or those based on Polyacrylic or Polyacrylmethylestern, polyvinyl acetate, polyvinyl chloride and mixtures thereof.
  • the impregnation can take place in a separate machine passage also in the size press or with a film press in the paper machine.
  • the impregnation or impregnation of the paper with the impregnating resin results in substantially no air pockets in the sheet.
  • the impregnating resin is distributed homogeneously in the sheet.
  • the proportion of the impregnating resin, calculated as solids, in the paper makes up from 10 to 40% by weight, based on the mass of the paper. Because, unlike in a conventional paper or even in a decorative paper in an impregnated paper substantially no air bubbles are present, called a decorative paper as a decorative film.
  • the impregnated papers can still be painted and printed and then applied to a substrate such as a wood panel.
  • Fig. 1 The opacity of the decorative paper after pressing with a pad depending on the amount of titanium dioxide when using a decoration base paper according to the invention with pigment resin particles (A) and außsdekorrohpapiers with the titanium dioxide preparation (C) is shown.
  • Ti-Pure® R-796 + Laminate Grade Titanium Dioxide Pigment, manufacturer DuPont with 158.75 g of deionized water and 1.4 g of Byk 154 (ammonium polyacrylate, Byk Altana) and dispersed with a ULTRA-TURRAX® Model T25 Rotor-Stator Dispersing System for five minutes at 10,000 revolutions per minute (RPM).
  • the dried resin-TiO 2 dispersion is solid and has an area of about 4x750 cm 2 . These chips must be pre-shredded manually before dry grinding. Here, sizes below 3 cm x 3 cm are targeted. Then the chips are dry-ground. For this purpose, the chips are placed in a 3 liter grinding container made of white ceramic (eg zirconium dioxide). In addition, the grinding balls, which are also made of white ceramic, in the container given ([number x ball diameter] 5x4 cm, 12x3 cm, 55x2 cm, 100x1, 5 cm, 165x0,9 cm). After the container has been sealed, it is placed on two rollers with one of the rollers driven by a motor. At a speed of 100 to 150 revolutions / min, the chips are dry-ground for 20 hours.
  • white ceramic eg zirconium dioxide
  • the grinding balls which are also made of white ceramic
  • Ti-Pure® R-796 + Laminate Grade Titanium Dioxide Pigment, manufactured by DuPont a ULTRA-TURRAX® model T25 rotor-stator dispersing system for five minutes dispersed at 10,000 revolutions per minute (rpm), the pH of the dispersion is then adjusted to 8.5 with 10% by weight sodium hydroxide solution.
  • adipic acid diethylenetriaminepichlorohydrin copolymer (Giluton® XP 14, BK Giulini GmbH) as wet strength agent are added to the distributor and the suspension is adjusted to pH 6 with 10% strength sulfuric acid.
  • the titanium dioxide preparations A or C are added (converted about 2 g of pure TiO 2 per sheet) and the suspension mixed with a paddle stirrer for 15 seconds. Thereafter, another 0.95 g of the 1.5% by weight adipic acid diethylenetriaminepichlorohydrin copolymer solution is added and the mixture is mixed for a further 45 seconds.
  • the single batch thus prepared is added to the filling chamber of the sheet former to 2 l of water, made up to 4 l total volume and the sheet forming process is started.
  • the individual sheets A1 to A 4 and from the comparative titanium dioxide dispersion C were prepared.
  • Impregnation and Compression of Inventive and Comparative Decorative Paper Sheets To impregnate the individual sheets, a solution containing 52% by weight of melamine-formaldehyde resin (KAURAMIN® 773 from BASF SE) in water containing 1.6% by weight of wetting agent (Hypersal® VXT 3797 of Surface Specialties Germany) and 0.8% by weight MADURIT® Hardener MH 835 / 70W, available from Ineos Melamines, Germany.
  • the decorative paper sheets are placed on the resin solution until fully soaked for at least 60 seconds and then completely immersed in the resin bath. Excess resin is then doctored off and the sheet dried at 130 ° C for 25 seconds. Thereafter, the sheet is again completely immersed in the resin solution, excess resin is again doctored off and dried at 130 ° C to a residual moisture content of 6 wt .-%.
  • the impregnated decor paper sheets are pressed by the high-pressure process (HPL) at a temperature of 140 ° C and a pressure of 234 bar with a 40x40 cm size plate for 4 minutes and cooled in the press to 60 ° C. Under the sheet to be tested, a much smaller black and a white decor paper sheet for measuring the opacity are pressed in at two different places.
  • HPL high-pressure process
  • the opacity of the decorative paper sheet to be tested is determined by measuring and comparing reflection densities.
  • a white and a black sheet are arranged side by side.
  • the sheet to be tested for opacity is laminated and laminated onto a plate.
  • the reflectance measurements over the white and over the black sheet were made with a Datacolor 600 colorimeter.
  • the reflection density determined over the black sheet was divided by the reflection density obtained over the white sheet, and the result was multiplied by 100.
  • the opacity of the decorative paper is applied after pressing against the surface-related titanium dioxide content.
  • the results of the opacity measurement show that the decorative papers containing the decorative base paper of the invention containing the pigment resin particles (titanium dioxide preparation A), at comparable titanium dioxide content have a significantly higher opacity than the decorative papers containing außsdekorrohpapier with the comparative preparation (titanium dioxide preparation C).
  • a decoration base paper according to the invention a saving of titanium dioxide of at least 50% of the amount can thus be achieved without the opacity of the decor paper deteriorating.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (10)

  1. Papier pour matériau de revêtement décoratif, qui contient des fibres de cellulose et des particules de résine pigmentaire, caractérisé en ce que les particules de résine pigmentaire contiennent un pigment exempt de substrat et une résine durcie et que la granulométrie moyenne des particules de résine pigmentaire est de 1 à 30 µm, sachant que le rapport volumétrique du pigment par rapport à la résine dans les particules de résine pigmentaire est de 1:1 à 1:10.
  2. Papier selon la revendication 1, caractérisé en ce que le papier est un papier brut décoratif.
  3. Papier selon revendication 1 ou 2, caractérisé en ce que les particules de résine pigmentaire sont dotées d'une granulométrie d'environ 3 µm.
  4. Papier selon la revendication 3, caractérisé en ce que le rapport volumétrique entre le pigment et la résine contenus dans les particules de résine pigmentaire est de 1:1,5 à 1:4.
  5. Papier selon l'une des revendications 1 bis 4, caractérisé en ce que le pigment est choisi parmi le kaolin, le carbonate de calcium, le sulfate de calcium, le sulfate de baryum, le dioxyde de titane, le talc, le silice, l'oxyde d'aluminium, l'oxyde de fer, le carbonate de calcium, dans sa forme naturelle, comme la pierre calcaire, le marbre ou la pierre dolomite, et les mélanges de ceux-ci.
  6. Papier selon la revendication 5, caractérisé en ce que le pigment est de l'oxyde de titane.
  7. Papier selon l'une des revendications 1 bis 6, caractérisé en ce que le rapport volumétrique de l'oxyde de titane par rapport à la résine contenue dans les particules de résine pigmentaire est de 1:7 à 1:3.
  8. Papier selon l'une des revendications 1 à 7, caractérisé en ce que la résine est choisie parmi la résine de mélamine formaldéhyde, la résine de mélamine urée formaldéhyde, la résine d'urée, la résine d'urée formaldéhyde et la résine phénol formaldéhyde et les mélanges de celles-ci.
  9. Papier selon la revendication 8, caractérisé en ce que la résine est une résine d'urée.
  10. Papier décoratif ou pellicule décorative contenant un papier pour matériaux de revêtement décoratif selon l'une des revendications 1 à 9.
EP14195070.9A 2014-11-27 2014-11-27 Papier à haut pouvoir couvrant Active EP3026175B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP14195070.9A EP3026175B1 (fr) 2014-11-27 2014-11-27 Papier à haut pouvoir couvrant
US14/941,977 US9976257B2 (en) 2014-11-27 2015-11-16 Paper with high covering power
JP2015231348A JP2016102288A (ja) 2014-11-27 2015-11-27 高い被覆力を有する紙
CN201510849841.4A CN105648838A (zh) 2014-11-27 2015-11-27 具有高遮盖力的纸

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP14195070.9A EP3026175B1 (fr) 2014-11-27 2014-11-27 Papier à haut pouvoir couvrant

Publications (2)

Publication Number Publication Date
EP3026175A1 EP3026175A1 (fr) 2016-06-01
EP3026175B1 true EP3026175B1 (fr) 2019-04-03

Family

ID=52133804

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14195070.9A Active EP3026175B1 (fr) 2014-11-27 2014-11-27 Papier à haut pouvoir couvrant

Country Status (4)

Country Link
US (1) US9976257B2 (fr)
EP (1) EP3026175B1 (fr)
JP (1) JP2016102288A (fr)
CN (1) CN105648838A (fr)

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Publication number Priority date Publication date Assignee Title
GB487835A (en) 1936-12-22 1938-06-22 Of Chemical Industry Soc Manufacture of improved pigments
GB1505641A (en) * 1974-04-19 1978-03-30 Grace W R & Co Process of preparing a filler composition for paper
DE3020854A1 (de) * 1980-06-02 1981-12-10 Lentia GmbH Chem. u. pharm. Erzeugnisse - Industriebedarf, 8000 München Fuellstoff fuer papier, karton oder pappe
US4608401A (en) 1982-09-02 1986-08-26 Union Carbide Corporation Method of encapsulating finely divided solid particles
US4495245A (en) * 1983-07-14 1985-01-22 E. I. Du Pont De Nemours And Company Inorganic fillers modified with vinyl alcohol polymer and cationic melamine-formaldehyde resin
JPS61133218A (ja) * 1984-12-04 1986-06-20 Mitsui Toatsu Chem Inc 紙用填料の製造方法
US4895759A (en) * 1988-03-18 1990-01-23 Ppg Industries, Inc. Saturating grade paper
JPH04370297A (ja) * 1990-11-15 1992-12-22 Mitsui Toatsu Chem Inc 紙用カチオン性複合粒子その製造法及びその利用
JPH04343792A (ja) * 1991-05-20 1992-11-30 Mitsui Toatsu Chem Inc 複合粒子の製造方法
FR2685704B1 (fr) * 1991-12-30 2002-06-14 Rhone Poulenc Chimie Nouvelles particules de dioxyde de titane, leur utilisation comme pigments opacifiants pour papiers et lamifies de papier.
ATE217373T1 (de) * 1996-02-29 2002-05-15 Oji Paper Co Mattgestrichenes papier und verfahren zu siener herstellung
DE19961964A1 (de) 1999-12-22 2001-06-28 Basf Ag Verfahren zur Herstellung einer wässrigen Dispersion von aus Polymerisat und feinteiligem anorganischen Feststoff aufgebauten Partikeln
DE10057294C5 (de) * 2000-11-17 2005-06-30 Technocell Dekor Gmbh & Co. Kg Dekorrohpapier mit hoher Opazität, sowie Dekorpapier oder Dekorfolie
JP2007270388A (ja) * 2006-03-31 2007-10-18 Oji Paper Co Ltd 印刷用艶消し塗被紙
DE102010051382A1 (de) * 2010-11-16 2012-05-16 Dekor-Kunststoffe Gmbh Verfahren zur Herstellung einer Basisschicht, insbesondere für die Bedruckung mittels digitaler Drucktechnik
DE102013100353A1 (de) 2012-01-12 2013-08-22 Bene_Fit Systems Gmbh & Co. Kg Reaktive Composites, bestehend aus einem Träger, TiO2 und einem Bindemittel, sowie deren Herstellung und Verwendung
CA2895946C (fr) * 2013-01-09 2020-10-20 E. I. Du Pont De Nemours And Company Papier decor ayant des performances optiques ameliorees et comprenant des particules inorganiques traites

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Also Published As

Publication number Publication date
JP2016102288A (ja) 2016-06-02
US9976257B2 (en) 2018-05-22
US20160153147A1 (en) 2016-06-02
EP3026175A1 (fr) 2016-06-01
CN105648838A (zh) 2016-06-08

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